DE1518087B2 - - Google Patents

Description

3 4

nut fat alcohol (or distilled coconut fat alcohol - a molar ratio of ethylene oxide to alkyl

hols) are very suitable. phenol from 10: 1 to 25: 1 is present; further condensation

The tertiary amine oxides according to the invention can be cation products of ethylene oxide and the

generally obtained by oxidation of the corresponding formation of propylene oxide and ethylenediamine

tertiary amine can be obtained. The corresponding 5th product.

tertiary amine can generally be obtained by alkylation. Inorganic framework salts, which are used alone or mixed with the respective secondary amine with a suitable one, are alkali metal carbonates, borates, long-chain alkyl compounds. If phosphates, polyphosphates, bicarbonates and silicates are required, the long-chain alkyl compound (ammonium or substituted ammonium salts can (e.g. a ketoalkane) are such that the ions can also be used.) Specific In the case of treatment (e.g. a reduction) of the tertiary amine, sodium tripolyphosphate plays a role in such salts, before the oxidation a hydroxyl group is introduced in the desired position of the R ^x group. The phosphate, sodium bicarbonate, potassium tripolyphosphate, examples illustrate such reactions. Potassium pyrophosphate, sodium hexametaphosphate, or alkyl glycidyl ethers (a starting trium sesquicarbonate, sodium mono- and di-ortho bond for the introduction of 3-alkoxy-2-hydroxyphosphate and potassium bicarbonate. Such an inorganic propyl group) is used in the CA PS 582 404 and niche framework salts further improve the cleaning described in US Pat. No. 2,989,547. effect of the respective amine oxides.

The compounds according to the invention are examples of organic framework salts, which alone or such valuable detergents and surfactants used mixed are alkali metal, am-agents. However, they are preferably used together with monium or substituted ammonium amino polyanders Materials for detergent preparations ver carboxylate, z. B. Sodium and potassium ethylenedioperates, which are used especially in solid form amine tetraacetate, sodium and potassium N- (2-hydroxybe, z. B. as pieces, flakes, granules or äthyO-ethylenediamine tetraacetate, sodium and Ka tablets. The tertiary amine oxides of the invention are lium nitrilotriacetate and sodium, potassium and tri cans also for the production of liquid detergent äthanolammonium-N- (2-hydroxyethyl) -nitrilodiacetelpräparaten be used. Such preparations would do. Mixed salts of these polycarboxylates can be used alike about 5 to 80% of the tertiary according to the invention can be used. Other organic framework salts that Ren amine oxides and about 95 to 20% anionic organic can be used are: Hydroxyäthyläthylenniche Detergents, non-ionic organic detergents, 30 diamine triacetate, 2-hydroxyethyliminodiacetate, dietary hygiene agents, water-soluble inorganic alkaline framework triamine pentaacetate, 1,2-diaminocyclohexane tetra salts, water-soluble organic alkaline complex acetate. The alkali metal salts of phytic acid, e.g. B. Forming frameworks or mixtures of these materials, sodium phytate, are also useful, contain. Preferred detergent preparations contain about

Granule or Flake Detergents 35 10 to 30% tertiary amine oxides according to the present invention preferably contain about 5 to 50% of the invention and at least an equal amount of sodium amine oxides and about 95 to 50% of the norma tripolyphosphate. Dimethyl-2-hydroxyl is preferred solid, water-soluble inorganic or dodecylamine oxide that has good leaching properties organic framework salts. Detergents in the form of, and in this regard, dimethyldodecylamine oxide Pieces contain about 5 to 50% which is superior to the invention. It is also an effective laziness Amine oxides when combined with anionic detergency builder for anionic non-agents such as B. a soap base can be used, soap detergents.

and, if desired, inorganic or organic. These detergent preparations can also contain any

Builders or inert fillers. Pieces can contain the usual additives, thinners or auxiliaries

if desired, contain about 40 to 80% of the agents according to the invention, moderate amine oxides as the only detergent component

contain, the remainder can be made of inert fillers and Example 1 Builders exist.

Anionic organic detergents alone or 5 moles of dimethylamine were taken under anhydrous

are used mixed, both actual 50 conditions can be achieved with the help of a dry ice-acetone cooler.

Soaps as well as other detergents. Examples of lers liquefied. 0.05 mol of anhydrous aluminum

suitable soaps are the sodium, potassium, ammoride were added to the dimethylamine and that

nium and alkylammonium salts of higher fat mixture in a cold glass autoclave insert (3 liters)

acids (C _{10 -C 20} ). Examples of anionic organic are given. One mole of Ci ₂ olefin oxide of the formula non-soap detergents are: Alkylglyceryläthersul- 55

fonates, alkyl sulfates, alkyl monoglyceride sulfates or C ₁₀ H ₂₁ CH-CH ₂

-sulfonate, alkylpolyethoxyether sulfate, acylsarkosi- O nate, acyl ester of isethionates, acyl-N-methyl-

tauride 'alkyl-benzenesulfonate, alkylphenol-poly- was added to the dimethylamine with mixing ethoxysulfonate. These compounds contain 60 and chilled. The insert was refrigerated in a

given the alkyl or acyl group 10 to 20 carbon autoclave. After closing the autoclave

atoms. They are in the form of water-soluble, the mixture was heated to 200 ° for 3 hours. Of the

Salts, for example as sodium, potassium, ammo-autogenic pressure was kept at 21 to 28 kg / cm ² ,

nium and alkylolammonium salt used. After cooling and blowing out the autoclave with N ₂

Examples of nonionic organic detergents 65 were the contents in an aqueous 10 percent HCl-

are: Polyethylene oxide condensates of alkylphenols, solution dissolved to remove the amine-aluminum

in which the alkyl group has 6 to 12 carbon atoms to hydrolyze chloride complex. The solution was

(e.g. 5-octylphenol) and the ethylene oxide made basic with solid KOH and the upper amine

layer subjected to vacuum distillation. It was a 70 percent yield of distilled dimethyl-2-hydroxydodecylamine obtain. Elemental analysis of the amine obtained had the following results (in %):

Calculated ... C 73.3, H 13.6, N 6.1, O7.0;
Found ... C 73.4, H 13.3, N 5.8, O 7.2.

The implementation is given by the following equation:

C ₁₀ H ₂₁ CH - CH ₂ + HN (CH ₃ ),

The dimethyl-2-hydroxydodecylamine was with a 10 percent excess of hydrogen peroxide in a mixture of water and ethanol of 1: 3 60 ° C oxidized. After extracting the unreacted amine with petroleum ether, the aqueous phase was in the Dried cold to give a pure white powdered amine oxide. The material was continued through Purified recrystallization from acetone. The yield of amine oxide from the oxidation and subsequent Purification was 95%.

The corresponding diethyl and dipropyl compounds can by using equivalents molar amounts of diethylamine or dipropylamine can be obtained by the method of Example 1.

20 parts of dimethyl-2-hydroxydodecylamine oxide will be with 50 parts of sodium tripolyphosphate and 30 parts of sodium sulfate to form a solid detergent preparation

Il

^ C ₉ H ₁₉ CCH ₃ -f HCHO + (CHg) ₂ NH · HCl

38 g of LiAlH ₄ were dissolved in 600 cm ^{3 of} anhydrous diethyl ether. 57 g of the 3-ketododecyldimethylamine obtained above were dissolved in 400 cm ^{3 of} diethyl ether and added dropwise to the LiAlH ₄ solution. This mixture was then ^{stirred for an additional I 1} Z ₂ hours. The unreacted LiAlH ₄ AlCl,

OH

C ₁₀ H ₂₁ CH - CH ₂ N (CH ₃ ) ₂

combined, which cleans well when washing and results in a good lye when washing dishes. The formation of lye of dimethyl-2-hydroxydodecylamine oxide in such a preparation is similar to that of sodium dodecylbenzenesulfonate when washing dishes Superior to the preparation.

Example 2

170 g of 2-undecanone, 22.5 g of paraformaldehyde and 40.8 g of dimethylamine hydrochloride were ^{mixed with 500 cm 3 of} ethanol and ^{stirred at 78 °} C. for 24 hours. The reaction mixture was acidified and extracted with ethyl ether to separate off the unreacted 2-undecanone. The mixture was then made alkaline and extracted again with ethyl ether; Yield of 3-keto-dodecyldimethylamine: 81 g. The implementation corresponds to the following equation:

Il

nC ₉ H ₁₉ CCH ₂ CH ₂ N (CH ₃ ) ₂ • HCl + H ₂ O

was decomposed by adding ethyl acetate and then water. The solution was filtered to solidify Separate material. The ether layer was evaporated on a steam bath, leaving the hydroxyamine was obtained. This implementation is represented by the following equation:

35

4n _{-C 9} H ₁₉ CCH ₂ CH ₂ N (CH ₃ ) ₂ + LiAlH ₄

4H ₂ O OH

-> 4 nC ₉ H ₁₉ CHCH ₂ CH ₂ N (CH ₃ ) ₂ + Al (OH) ₃ + LiOH

Calculated ... amine number 244, hydroxyl number 244; found ... amine number 240, hydroxyl number 227.

45 g of the dimethyl-3-hydroxydodecylamine were mixed with 8.5 g of hydrogen peroxide (28.5 g of a 30 percent aqueous solution) and 250 cm ^{3 of} ethanol and 125 cm ^{3 of} water. This mixture was stirred at 50 ° C. for 6 hours. After cooling to room temperature, the solution was ^{diluted with 400 cm 3 of} water and the remaining peroxide was catalytically decomposed. The unreacted amine was separated off by a threefold ether extraction. Most of the ethanol was evaporated from the solution on a steam bath and the product recovered by drying in the cold. The amine oxide was recrystallized from acetone and gave the following elemental analysis (in%):

Calculated ... C 68.50, H 12.73, N 5.71; Found ... C 67.89, H 12.30, N 5.67.

The obtained dimethyl 3-hydroxydodecylamine oxide was tested for hygroscopicity by treating it with the 2-hydroxydocecyldimethylamine oxide according to Example 1 and compared with a non-OH-substituted dimethyldodecylamine oxide. The hygroscopicity was determined by dry crystallized material in a chamber at 21 ° C with a: brought constant relative humidity of 50%

sample OH Weight
increase
after
ITag Weight
increase
after
7 days nC ₁₀ H ₂₁ CHCH ₂ N (CH ₃ ) ₂
Ψ
O OH 8.4% 11.7% nC ₉ H ₁₉ CHCH ₂ CH ₂ N (CH ₃ ) ₂
Φ
O nC ₁₂ H ₂₅ N (CH ₃ ) ₂
Φ
O 9.9% 10.7% 32% 30%

It turns out that the 3-hydroxydodecyl compound and the 2-hydroxydodecyl compound are less hygroscopic are as the unsubstituted dodecyl compound.

The heat resistance of the compounds according to the invention is indicated by the decomposition temperatures of the 3-Hydroxydodecylverbindung and the 2-Hydroxydodecylverbindung which lie at 145-130 ⁰ C, while the decomposition temperature of the unsubstituted Dimethyldodecylaminoxids at HO ⁰ C is located.

The dimethyl-S-hydroxydodecylamine oxide and the Dimethyl-2-hydroxydodecylamine oxide were examined for their cleaning effect. These were amine oxides Essentially equivalent to sodium dodecylbenzenesulfonate in terms of its cleaning effect. This was done by washing naturally soiled swatches (unfinished printed fabrics) in one Ojl% aqueous solution of a mixture of 20% of the respective organic detergent compound (Amine oxide or alkylbenzenesulfonate), 50% sodium tripolyphosphate and 30% sodium sulfate determined. The preparation had a pH of 10, and · washing was done for 10 minutes at 54 ° C using a wash water which is a Had a hardness of 0.1119 g / l. The detergency was determined by measuring the percentage of greasy Soil that remained on a standard size (dry basis) swatch after washing was. The percentage of greasy soil after washing with the amine oxide test preparation was compared with the percentage after washing with the conventional alkylbenzenesulfonate preparation remained. The lower the percentage based on the percentage remaining the greasy dirt, the better the cleaning effect. For washing there was a Tergotometer used. (Tests with a

Tergotometers are described in »Detergency Evaluation and

Testing "by J. C. Harris, edited by

Interscience Publishers, Inc., New York, N.Y. [1954],

P. 60.).

Diethyl 2-hydroxytetradecylamine oxide and a di-

methyl-2-hydroxyalkyl-amine oxide, in which the alkyl derived from a coconut fatty alcohol can be prepared analogously to the processes of Examples 1 and 2 will. These compounds have essentially the same heat resistance and hygroscopicity,

and the cleaning effect is slightly weaker than that the hydroxy-dodecyl compound.

B e i s ρ i e 1 3

1.818 g of dodecyl glycidyl ether were placed in a 2 liter autoclave. Air was displaced from the head by dimethylamine. The autoclave was then heated ^{to 199 ° C.} A pressure of 32 kg / cm ² was obtained in the autoclave by

Filled dimethylamine under nitrogen pressure. During the implementation of the ether with the dimethylamine such a valve setting was made that a constant pressure and a constant temperature were maintained. After 1 hour the

Autoclave cooled. The obtained N.N-dimethyl-3-dodecoxy-2-hydroxy-n-propylamine contained about 25/1

dissolved dimethylamine, which was distilled off at 5 torr and 79.degree. The amination is carried out by the following Equation described:

^0H

C ₁₂ H ₂₅ OCH ₂ - CH - CH ₂ + HN (CH ₃ ), - »C ₁₂ H ₂₅ OCH ₂ - CH - CH ₂ N (CH ₁ Oi

1000 g of this tertiary amine were mixed with 2789.3 g of water, heated to 82 ° C. and mixed with 462 g of 25 percent hydrogen peroxide solution while stirring vigorously. The mixture obtained was ^{aged at 77 °} C. overnight in order to decompose excess peroxide.

The N, N-dimethyl-3-dodecoxy-2-hydroxy-n-propylamine oxide obtained absorbed only 0.3% of water after storing it in an open vessel at room temperature and room conditions for a week had been. Under extreme storage conditions of 32 ° C and 80% relative humidity for 7 days only 22% water was absorbed. This amine oxide showed excellent cleaning power and lye formation, and it was excellent in heat resistance.

N, N - diethyl - 3 - tetradecoxy - 2 - hydroxy - η - propyl amine oxide can be obtained analogously to the procedure of Example 3. This connection has compared to the Dodecyl compound improved properties.

The tertiary amine oxides according to the invention can be used in detergent preparations with improved hygroscopicity and heat resistance can be used. Such detergents can, for. B. the following composition to have:

Granular detergent

Dimethyl-2-hydroxydodecyl-

amine oxide 0 /

Sodium sulfate n ° /

Sodium tripolyphosphate 2 ο /

Sodium silicate "/ °

Water 3.5 / year

Granular detergent

Diethyl 2-hydroxydodecyl amine oxide .. 10%
Sodium dodecylbenzenesulfonate (the
Dodecyl group comes from tetrapro-

Pylene) \ φ

Sodium trilotnacetate ■ " ζ °

Sodium sulfate «0 /

Water ^ / _o

Granular detergent

Di-n-propyl-S-hydroxy-tetradecyl-

amine oxide * '°

Condensation product of 1 mole of nonylphenol and 9 moles of ethylene oxide ... 10 / _Q

Sodium Pyrophosphate · ^ O / b

409 584/415

9 10

Sodium carbonate 3% In order to ensure the compatibility of the inventive

Trisodium phosphate 3% bonds compared to trialkylamine oxides without

Sodium sulfate adds 24% hydroxyl groups in the long chain R ^{x residue}

. show, dimethyldodecylamine oxide and di-

Granular detergent ₅ methyl ^ -hydroxydodecyl-amine oxide on guinea pig

Dimethyl-2-hydroxydodecyl amine oxide particles tested.

Potassium ethylenediamine tetraacetate 2 parts In this test, guinea pigs whose

. Undersides to the thorax had been shaved in

Granular detergent is _a 0.2 percent solution of the material to be tested

Dimethyl-3-hydroxydodecyl amine oxide part io at 37 ° C for 4.5 hours a day on three

Potassium pyrophosphate immersed for 5 parts consecutive days. The animals are

Spray-dried granular detergent classified for three days after the last immersion

N ^ -DimethyW-dodecoxy ^ -hydroxylated. The classes result from the average

n-propyl amine oxide 5% results in no fewer than three animals. One

Sodium Dodecylbenzenesulfonate 15% 15 rating scale from 1 to 10 is used to evaluate the

Sodium tripolyphosphate 50% to classify effects that occur with prolonged exposure to the

Sodium sulfate 15% test solution can be applied to the animal's skin.

Sodium silicate 5% number 10 denotes the ideal or flawless

Moisture 10% skin (soft, smooth and flexible) and the effect of a

... 20 theoretically sound detergent. Number 1

The toilet side wall draws attention to severely irritated skin. Embody other values

Diethyl 3-hydroxytetradecyl amine oxide. 10% the gradations between these extreme values.

Sodium coconut oil soap 15% number 1 means strong in the guinea pig test

Sodium tallow soap. ' 60% thickened, dry, cracked and bleeding skin,

Triäthanolammoniumäthylenediamine- 25 d. H. extreme irritation. (Number 1 would be

tetraacetate 5% induced severe reddening of human

Moisture 10% lead to dryness and dryness of the skin. An over-

_ ^,., ..... moderately long test time in guinea pigs leads to

Poured toilet soap stump results in far more extreme results than with men

See dimethyl-2-hydroxydodecyl-amine oxide 5% 30.) Between the test results at marine

Sodium Dodecylbenzenesulfonate 57% piglets and those in normal tests in humans

Glyceryl tristearate 38% resulting effects, there is a good correlation

. tion; On the guinea pig test one can look at scouring detergents for the degree of relative compatibility of the Silica flour 85% 35 detergents for human skin Combined detergent made from 85% trisodium. In the guinea pig test, had dimethyl phosphate and 15% dimethyl-3-hydodecylamine oxide rating 2, while dimethyldroxy-tetradecylamine oxide 15% 2-hydroxydodecylamine oxide was 5.

Claims (3)

1 2 in which R1 for a 2-hydroxyalkyl, 3-hydroxy claims: alkyl or 3-alkoxy-2-hydroxypropyl group, the alkyl and alkoxy radicals having chain lengths of 12 to 1. Tertiary amine oxides of the formula have 14 carbon atoms, and R ² and R ^{3 represent} R ¹ R ² R ³ N -> O ⁵ methyl, ethyl, n-propyl or isopropyl groups stand. in which R ^{1 stands} for a 2-hydroxyalkyl, 3-hydroxy- The compounds described above alkyl or 3-alkoxy-2-hydroxypropyl group, where- in the following for the sake of simplicity in the writing in the case of the alkyl and alkoxy radicals, chain lengths of 12 are shown as R ¹ R ² R ³ N - ^ - O, to 14 carbon atoms, and R ² and R ³ for io examples of the compounds according to the invention Methyl, ethyl, n-propyl or isopropyl groups are dimethyl-2-hydroxydodecyl amine oxide, diethyl stand. S-hydroxydodecyl amine oxide ^ imethyl ^ -hydroxytetra- 2. Tertiary amine oxides according to claim 1, da- decyl amine oxide, diethyl 2-hydroxytetradecyl amine characterized in that R ² and R ^{3 are} methyl radicals oxide, diisopropyl-2-hydroxydodecyl amine oxide, N, N-. 15 dimethyl-S-dodecoxy ^ -hydroxy-n-propylamine oxide, 3. Use of the tertiary amine oxides according to NjN-diethyl-S-tetradecoxy ^ -hydroxy-n-propylamine claims 1 and 2 as detergent substance oxide and methylethyl-3-hydroxydodecylamine oxide.
Zen. The tertiary amine oxides are considered a large group known of connections. Surprisingly However, it was found that those trialkyl amine oxides which, as described above, have particularly arranged hydroxyl groups (ie in the radical R ¹ With the constant improvement of organic detergents - a hydroxyl group in the 2- or 3-position), it has been found that certain characteristics of organic detergents, particularly desirable ones, are extremely important. To these characteristics stores have, ie a better compatibility, belongs to the resistance to components that show hygroscopicity and heat resistance,
The water hardness are responsible, a high cleaning effect, however, only certain tertiary amine oxides appear to have the above-mentioned properties and the ability of soaps for hard soaps to have the properties listed above. Waters such as B. calcium soap to make soluble. Although, in these particular amine oxides, R ¹ , R ² must be equal to a number of organic detergents 30 and R ³ are as defined above, which have these properties, there is a greater ^{if the alkyl or alkoxy group in R 1} Detergents that have even more desirable intrinsic or smaller chain lengths will have broader uses. te detergent effect not achieved. Likewise, the The heat resistance is an important inherent - desirable detergent properties are not preserved, that many detergents lack. This resistance ^{- if R 2} and R ^{3 have} more than three carbon atoms, Speed is particularly desirable when the detergent The long-chain R ^x radical must be in the 2- or 3-position gentien during use or during their manufacture (i.e. on the second or third carbon atom from Position, for example in spray drying, a nitrogen atom counted) a hydroxyl group has Exposed to heat. ben to the inventively improved properties - Another advantageous property of an organic 40 in terms of compatibility, hygroscopicity and see detergent is low hygroscopicity to maintain heat resistance. Is the leads to improved crystallinity. If upper hydroxyl group in the R ^ radical in the 1- or «-position, surface-active detergents that are hygroscopic, the corresponding amine oxide compound is unaffected. in the form of pieces or granules. The 3-alkoxy-2-hydroxy-n-propyl radical has R ¹ den, then the desired physical properties are 45 the following formula
properties impaired. Pieces become soft and boggy, and granules tend to collapse together- ROCH ₂ CHCH ₂ - bake, they lose their free flowability and their I. good solving skills. For example, it was found OH the fact that trialkylamine oxides are an excellent 50 Detergents, but are so hygroscopic that they have a chain length of 12 to 14 carbon atoms can only be used effectively in liquid form. The 2-hydroxyalkyl, 3-hydroxyalkyl can. and 3-alkoxy-2-hydroxy-n-propyl compounds It has now been found that a group of approximately the same reduced hygroscopicity in the vertical amine oxides of the following structure is identical to that of the corresponding compound which is used as R ¹ as preparations which preferably have these compounds in the non-hydroxyl-substituted alkyl group. The 3-Hyfester form contains, excellent self-washing hydroxyalkyl compound, has about the same water properties and better skin tolerance, solubility, as the corresponding, non-OH-sub, improved heat resistance and a low-substituted R ¹ -alkyl group-containing compound, show hygroscopicity . 60 while the water solubility of the 2-hydroxyalkyl The subject of the present invention are tertiary bonds somewhat lower than the solubility of the corresponding Amine oxides of the formula corresponding compound with non-OH-substituted R ¹ - R2 group is. In the tertiary amine oxides according to the invention _R1 '65 R ¹ can be from naturally occurring fats and oils I "*" or from synthetic starting materials such as. B. I originate from olefins. Mixtures of amine oxides R ³ where R ^{1 is} the alkyl or alkoxy group of a coconut